JP4040957B2 - Silica-containing cosmetics - Google Patents

Description

【０１２３】
（ｄ）評価方法
得られたO/W型サンスクリーンクリームの性能試験における評価方法は、以下のとおりである。
【０１２４】
（イ）化粧持続性：
O/W型サンスクリーンクリームを塗布して、ガラスプレートに２０μｍの厚みの塗布膜を形成し、室温にて１５分間乾燥後、水流下に１０分間放置後、状態を観察し下記基準により評価した。
【０１２５】
〇：状態変化が見られない。
△：僅かに剥離している。
×：完全に剥離している。
【０１２６】
（ロ）塗布時の伸び：
O/W型サンスクリーンクリームによりパネラー１０名による使用テストを行い、下記の＜５段階絶対評価＞を行い、その平均点をさらに下記の＜４段階評価＞にて行った。
【０１２７】
＜５段階絶対評価＞
（評 点）
良 い ： ５ 点、
やや良い ： ４ 点、
普 通 ： ３ 点、
やや悪い ： ２ 点、
悪 い ： １ 点
【０１２８】
＜４段階評価＞
（評点）
◎： ４点以上、
○： ３点以上４点未満、
△： ２点以上３点未満、
×： ２点未満
【０１２９】
（ハ）密閉感：
パネラー１０名による使用テストを行い、塗布後２〜３時間後に各項目について、下記の＜５段階絶対評価＞を行い、その平均点をさらに上記の＜４段階評価＞にて行った。
【０１３０】
＜５段階絶対評価＞
（評 点）
密閉感等が全くない： ６ 点、
密閉感等がない： ５ 点、
密閉感等が普通にある： ３ 点、
密閉感等がややある： ２点、
密閉感等が常にある： １ 点
【０１３１】
（ニ）べとつき：
上記（ハ）と同様に、パネラー１０名による使用テストを行い、同様に評価した。
【０１３２】
（ホ）つっぱり感：
上記（ハ）と同様に、パネラー１０名による使用テストを行い、同様に評価した。
【０１３３】
【表２】

【０１３４】
（ｅ）結果と考察
O/W型サンスクリーンクリームのような、一般的にO/W型乳化物は、外相が油相となるw/o型より使用性が優れるという利点があるが、一方、外相が水相であるため、汗などによる化粧持続性に問題がある。そのため、化粧持続性を向上させるため、通常皮膜形成性高分子が配合されるが、あまり配合すると密閉感、べとつき、つっぱり感等の使用性が悪化するため、従来、当該使用性との兼ね合いで、十分満足いく量を配合することが出来なかった。
【０１３５】
本発明によれば、かかる皮膜形成性高分子の添加量をあまり増加させなくても、O/W型乳化物の使用性での特性を維持したまま、従来の問題点である化粧持続性を改良することが出来ることが確認された。
【０１３６】
また、本発明における葉状シリカ２次粒子は、それ自身皮膜形成性を有するものであり、かつ、当該皮膜は、無機物による皮膜であるため、従来の高分子の皮膜とは異なり、塗布後２〜３時間経過しても、さらっとした仕上がりであり、密閉感、べとつき、つっぱり感がない。
【０１３７】
〔実施例５〕（油性ケーキファンデーション）
参考例３で製造した葉状シリカ２次粒子（粉末）を添加した場合について油性ケーキファンデーションを調製し、評価した。
【０１３８】
（ａ）処方
表３に示す処方に従った。
【０１３９】
（ｂ）製造方法
表３中の配合成分（１）〜（６）を均一に粉砕する。次ぎに配合成分（７）〜（1５）を加熱混合し、成分（１）〜（６）を加え均一に撹拌する。
撹拌物を脱泡後、トレイに流し込み、室温まで徐冷して、目的の油性ケーキファンデーションを得る。
【０１４０】
（ｃ）結果と考察
本発明による油性ケーキファンデーションは、良好な化粧持続性を有し、伸びがよく、かつ、基本的にそれ自身皮膜形成能を有する葉状シリカ２次粒子の皮膜が形成されるため、ワックス皮膜特有の油っぽい使用感がなく、塗布後２〜３時間ご経過しても、密閉感、べとつき、つっぱり感がない、さらっとした仕上がりであった。
【０１４１】
【表３】

【０１４２】
〔実施例６〕（O/W型乳化ファンデーション）
参考例２で製造した葉状シリカ２次粒子（水分散液）を添加した場合についてO/W型乳化ファンデーションを調製し、評価した。
【０１４３】
（ａ）処方
表４に示す処方に従った。
【０１４４】
（ｂ）製造方法
表４中の配合成分（１）〜（７）を加熱溶融し、これに撹拌混合した成分（８）〜（９）を加え均一に分散する。これに、加熱溶融した成分（１０）〜（１６）を徐々に加えて乳化を行い、室温まで撹拌冷却して、目的のO/W型乳化ファンデーションを得る。
【０１４５】
（ｃ）結果と考察
本発明によるO/W型乳化ファンデーションは、伸びが良く、O/W型であるにも関わらず、自己皮膜形成性を有する葉状シリカ２次粒子の無機皮膜による良好な化粧持続性を有し、塗布後２〜３時間後経過しても、密閉感、べとつき、つっぱり感がない、さらっとした仕上がりであった。
【０１４６】
【表４】

【０１４７】
〔実施例７〕（アイライナー）
参考例２で製造した葉状シリカ２次粒子（水分散液）を添加した場合についてアイライナーを調製し、評価した。
【０１４８】
（ａ）処方
表５に示す処方に従った。
【０１４９】
（ｂ）製造方法
表５中の配合成分（１）〜（８）を加熱溶融し、これに撹拌混合した成分（９）〜（１０）を加え均一に分散した後、冷却して、目的のアイライナーを得る。
【０１５０】
（ｃ）結果と考察
本発明によるアイライナーは、汗や涙などに対して強固な化粧膜を維持し、伸びが良く、自己皮膜形成性を有する葉状シリカ２次粒子の皮膜により、酢酸ビニル樹脂エマルションの密閉感、べとつき、つっぱり感が改善され、さらっとした仕上がりであった。
【０１５１】
【表５】

【０１５２】
〔実施例８〕（口紅）
参考例３で製造した葉状シリカ２次粒子（粉末）を添加した場合について口紅を調製し、以下の以下のごとく評価した。
【０１５３】
（ａ）処方
表６に示す処方に従った。
【０１５４】
（ｂ）製造方法
表６中の配合成分（１）〜（１１）を加熱溶融混合し均一に撹拌する。
撹拌物を脱泡後、モールドに流し込み、急冷し、目的の口紅を得る。
【０１５５】
（ｃ）結果と考察
本発明による口紅は、衣服やカップなどへ移りにくく、密閉感、べとつき、つっぱり感がなく、さらっとした仕上がりであった。
【０１５６】
【表６】

【０１５７】
〔実施例９〕（溶剤型ネイルエナメル）
参考例４で製造した葉状シリカ２次粒子（ＭＩＢＫ分散液）を添加した場合について溶剤型ネイルエナメルを調製し、評価した。
【０１５８】
（ａ）処方
表７に示す処方に従った。
【０１５９】
（ｂ）製造方法
表７中の配合成分（１）〜（１１）を均一に混合し、これに成分（１２）〜（１７）を添加し均一に分散し、目的の溶剤型ネイルエナメルを得る。
【０１６０】
（ｃ）結果と考察
本発明による溶剤型ネイルエナメルは、ＪＩＳ ５６００の鉛筆強度測定法により鉛筆強度を測定した結果、葉状シリカ２次粒子未配合品と比較し、耐久性が著しく向上することが確認された。また、皮膜形成性の樹脂を配合した場合と異なり、糸引きがないため、伸びが良く、形成した皮膜は、酸素透過性に優れるため、密閉感がなく、さらっとした仕上がりであった。
【０１６１】
【表７】

【０１６２】
〔実施例１０〕（W/O型マスカラ）
参考例３で製造した葉状シリカ２次粒子（粉末）を添加した場合についてW/O型マスカラを調製し、評価した。
【０１６３】
（ａ）処方
表８に示す処方に従った。
【０１６４】
（ｂ）製造方法
表８中の配合成分（１）〜（２）を加熱溶融し、これに撹拌混合した成分（３）〜（５）を加え均一に分散する。これに加熱溶融した（６）〜（８）を徐々に加え乳化を行い、室温まで撹拌冷却し、さらに（９）を加え、全体を均一として、目的のW/O型マスカラを得る。
【０１６５】
（ｃ）結果と考察
本発明によるW/O型マスカラは、汗や涙などに対して強固な化粧膜を維持し、伸びが良く、自己皮膜形成性を有する葉状シリカ２次粒子の皮膜により、W/O乳化型特有の密閉感、べとつきを改善し、さらっとした仕上がりであった。
【０１６６】
【表８】

【０１６７】
〔実施例１１〕（ヘアジェル）
参考例２で製造した葉状シリカ２次粒子（水分散液）を添加した場合について、ヘアジェルを調製し、評価した。
【０１６８】
（ａ）処方
表９に示す処方に従った。
【０１６９】
（ｂ）製造方法
表９中の配合成分（１）、（３）を（１０）の一部に分散させる。また、成分（１０）の残部に、成分（２）、（４）〜（９）を溶解する。両者を撹拌下に混合して目的のヘアジェルを得る。
【０１７０】
（ｃ）結果と考察
本発明によるヘアジェルは、毛髪への伸び及び皮膜形成性の葉状シリカ２次粒子の造膜効果によりヘアスタイリングを維持し、水溶性高分子独特のべとつきを軽減しさらっとした仕上がり感となった。
【０１７１】
【表９】

【０１７２】
〔実施例１２〕（化粧水）
参考例２で製造した葉状シリカ２次粒子（水分散液）を添加した場合について、化粧水を調製し、評価した。
【０１７３】
（ａ）処方
表１０に示す処方に従った。
【０１７４】
（ｂ）製造方法
表１０中の配合成分（１）〜（１０）を室温で均一に撹拌・混合し、目的の化粧水を得る。
【０１７５】
（ｃ）結果と考察
本発明による化粧水の基本的な効果は、皮膜形成性を有する葉状シリカ２次粒子の造膜効果による化粧持続性であり、化粧水に配合することで当該葉状シリカ２次粒子の密閉効果と、さらに当該葉状シリカ２次粒子表面シラノール基に若干の水分を保持することで、保水性に優れ、さらっとした仕上がり感となることが確認された。
【０１７６】
【表１０】

【０１７７】
〔実施例１３〕（クリーム）
参考例２で製造した葉状シリカ２次粒子（水分散液）を添加した場合について、クリームを調製し、評価した。
【０１７８】
（ａ）処方
表１１に示す処方に従った。
【０１７９】
（ｂ）製造方法
表１１中の配合成分（１）〜（７）を加熱溶融する。これに成分（８）〜（１３）を徐々に添加して乳化し、室温まで冷却して目的のクリームを得る。
【０１８０】
（ｃ）結果と考察
本発明によるクリームは、実施例１２記載の化粧水と同様に、その基本的な効果は、皮膜形成性を有する葉状シリカ２次粒子の造膜効果による化粧持続性であり、クリームに配合することで当該葉状シリカ２次粒子の密閉効果と、さらに当該葉状シリカ２次粒子表面シラノール基に若干の水分を保持することで、保水性に優れ、さらっとした仕上がり感となることが確認された。
【０１８１】
【表１１】

【０１８２】
〔実施例１４〕（ピールオフパック）
参考例２で製造した葉状シリカ２次粒子（水分散液）を添加した場合について、ピールオフパックを調製し、評価した。
【０１８３】
（ａ）処方
表１２に示す処方に従った。
【０１８４】
（ｂ）製造方法
表１２中の配合成分（１）〜（８）を加熱混合する。これに撹拌混合した成分（９）〜（１０）を添加し、均一に分散する。当該分散物に、成分（１１）〜（１３）を加えて加熱溶解後、室温まで冷却する。さらに、成分（１４）を添加して全体を均一にし、目的のピールオフパックを得る。
【０１８５】
（ｃ）結果と考察
本発明によるピールオフパックは、皮膜形成性の葉状シリカ２次粒子の有する造膜効果により、強い皮膜が得られると共に、実施例１２記載の化粧水同様、ピールオフパックに配合することで当該葉状シリカ２次粒子の密閉効果が付与され、また、葉状シリカ２次粒子表面シラノール基に若干の水分を保持することで、保水性に優れ、しっとりした使用感が得られた。
【０１８６】
【表１２】

【０１８７】
〔実施例１５〕（洗顔フォーム）
参考例３で製造した葉状シリカ２次粒子（粉末）を添加した場合について洗顔フォームを調製し、評価した。
【０１８８】
（ａ）処方
表１３に示す処方に従った。
【０１８９】
（ｂ）製造方法
表１３中の配合成分（１）〜（１１）を加熱混合し均一に溶解する。これに成分（１２）〜（１４）を添加し、室温まで冷却する。その後適用な容器に充填し、目的の洗顔フォームを得る。
【０１９０】
（ｃ）結果と考察
本発明による洗顔フォームは、泡立ちが良く、使用性、経時安定性のいずれも良好であった。
【０１９１】
すなわち、本発明による洗顔フォームの基本的な効果は、配合した皮膜形成性の葉状シリカ２次粒子の造膜効果による化粧持続性であるが、さらに配合された当該シリカ２次粒子間の間隙に空気を抱き込み、あわ立ちがよくなるため、洗浄後のヌルツキが少なく、さっぱりとした使用感となった。
【０１９２】
なお、特許文献１には、球状シリカを配合することによる同様の効果が記載されているが、本発明の洗顔フォームのほうがずっと泡立ち使用感共に良好であった。
【０１９３】
【表１３】

【０１９４】
〔実施例１６〕（シャンプー）
参考例３で製造した葉状シリカ２次粒子（粉末）を添加した場合についてシャンプーを調製し、評価した。
【０１９５】
（ａ）処方
表１４に示す処方に従った。
【０１９６】
（ｂ）製造方法
表１４中の配合成分（１）〜（９）を加熱混合し均一に溶解して室温まで冷却し、目的のシャンプーを得る。
【０１９７】
（ｃ）結果と考察
本発明によるシャンプーは、実施例１５の洗顔フォームと同様に泡立ちが良く、使用性、経時安定性のいずれも良好であった。
【０１９８】
すなわち、実施例１５の洗顔フォームと同様に、配合された当該シリカ２次粒子間の間隙に空気を抱き込み、あわ立ちがよくなるため、洗浄後のヌルツキが少なく、さっぱりとした使用感となった。
【０１９９】
なお、特許文献１に球状シリカを配合することによる同様の効果が記載されているが、本発明のシャンプーのほうが泡立ち使用感共に良好であった。
【０２００】
【表１４】

【０２０１】
【発明の効果】
本発明の化粧料には、上記実施例にも示したように、自己造膜性を有する葉状シリカ２次粒子が配合されているため、従来問題となっている皮膜形成性高分子物質特有の密閉感による厚ぼったさ、べとつき、つっぱるなどの使用感が大幅に改善され、本発明に従えば、化粧持続性、使用性に優れた化粧料が提供される。[0001]
BACKGROUND OF THE INVENTION
The present invention relates to cosmetics, and more particularly, has makeup persistence, high oxygen permeability of the film, has an elongation at the time of application, and is moist, thick and non-sticky even after several hours of application. Further, the present invention relates to a cosmetic material that does not stretch and has excellent usability.
[0002]
[Prior art]
Conventionally, various film forming agents have been used in cosmetics such as sunscreen agents, foundations, lipsticks, mascaras, eyeliners, nail enamels, etc., in order to prevent the makeup from being lost or transferred. This is because the cosmetic film of these cosmetics is likely to cause makeup transfer such as twisting and bleeding due to sweat, sebum, peeling off due to friction of hands and clothes, adhesion to cups and tobacco, etc. This is because a product with good makeup is desired from the viewpoint of usability and prevention of daily ultraviolet rays. In particular, in the hot and humid summer and sports, there is a craving for water resistance and makeup lasting. Therefore, synthetic resin emulsions and oil-soluble resins having a film-forming ability have been used for the purpose of preventing such makeup collapse.
[0003]
However, although synthetic resin emulsions and oil-soluble resins blended in cosmetics have the effect of preventing makeup collapse to some extent by the film formed, the film made of the synthetic resin originally has poor oxygen permeability. For this reason, when a large amount of this is blended in cosmetics, smooth skin respiration is hindered by the film formed on the skin surface. Ironically, instead of pursuing creativity and whitening, women who have carefully applied makeup will not be able to obtain the aesthetics, comfort, and peace of mind that are the main objectives of makeup. Because of the membrane, there was a big problem that we had to put up with a heavy and uncomfortable feeling of pressure.
[0004]
In this way, the more the amount of resin blended is increased for the purpose of better makeup retention, etc., the elongation of the cosmetic at the time of application (makeup) becomes worse, and an unpleasant stickiness after several hours of application. The contradiction that the skin is stretched because it is a strong film (stretching feeling), etc., has become a problem that cannot be overlooked in terms of touch and sensuality for women who make up.
[0005]
Conventionally, in cosmetics such as sunscreen creams, foundations, facial cleansing foams, shampoos, etc., it is well known that silica, particularly spherical silica, is blended and used in cosmetics as a filler in order to improve the feeling of finish and feel. (Patent Document 1, Patent Document 2). However, the spherical silica can give a certain feeling of use to the cosmetics, but since it does not have the ability to form a film itself, it basically has almost no effect on preventing makeup collapse. There wasn't. Moreover, the above-mentioned problems such as a feeling of tension due to the use of a large amount of a synthetic resin emulsion or the like are hardly improved.
[0006]
[Patent Document 1]
Japanese Patent No. 2924428
[Patent Document 2]
JP 7-242125 A
[0007]
[Problems to be solved by the invention]
Thus, the object of the present invention is to have makeup persistence, high oxygen permeability of the film, good elongation at the time of application, even after several hours of application, it is not thick, moist, non-sticky and does not stretch To provide cosmetics.
[0008]
As a result of diligent investigations from such a viewpoint, the present inventors have proposed this because the foliar silica having a specific flaky shape, which the inventors previously proposed, has the ability to form a high film. By blending in cosmetics, it is possible to impart high cosmetic sustainability to the cosmetics due to its self-forming properties, while basically eliminating the need to use a large amount of the synthetic resin emulsion. The present invention was completed by discovering that a high oxygen permeability, good elongation at the time of application, and a few hours after application, a cosmetic material that is not thick, moist, non-sticky, and sticky can be realized.
[0009]
[Means for Solving the Problems]
That is, according to the present invention, the following inventions are provided.
[0010]
[1] A cosmetic comprising the flake primary particles of scaly silica, the surface of which is aligned in parallel with each other, and a plurality of leaf-like silica secondary particles formed by overlapping.
[0011]
[2] The cosmetic according to [1], wherein the thickness of the secondary silica particles blended in the cosmetic is 0.001 to 3 μm, and the aspect ratio is at least 10 or more.
[0012]
[3] The cosmetic according to [1], wherein the leaf-like silica secondary particles to be blended in the cosmetic are powdery.
[0013]
[4] The cosmetic according to [1], wherein the leaf-like silica secondary particles blended in the cosmetic are in the form of a slurry dispersed in water at a concentration of 1 to 30% by mass.
[0014]
[5] The cosmetic material according to [1], wherein the secondary silica particles blended in the cosmetic material are in the form of a slurry dispersed in an organic medium at a concentration of 1 to 20% by mass.
[0015]
[6] The cosmetic according to any one of [1] to [5], further comprising one or more polymer substances having film-forming ability.
[0016]
DETAILED DESCRIPTION OF THE INVENTION
Hereinafter, the present invention will be described in detail.
[0017]
A feature of the present invention is that, as a filler for cosmetics, a specific form of silica having a self-forming property, that is, flake primary particles of flake silica are oriented in parallel with each other in a plurality of planes. It exists in the point which mix | blends the leaf-like silica secondary particle formed by overlapping.
[0018]
(Foliated silica secondary particles)
First, the secondary silica particles used in the present invention will be described.
The secondary particles of the leaf-like silica particles are substantially composed of the leaf-like silica formed by superposing the plurality of sheets with the primary particles being the basic constituent units and the surfaces of the primary particles being oriented parallel to each other. And foliar silica having a particle structure of a laminated structure.
[0019]
The flake primary particles are extremely thin scaly silica having a thickness of 0.001 to 0.1 μm. Such flake primary particles form leafy silica secondary particles in which one or a plurality of layers are aligned in parallel with each other in plane, and the thickness of the secondary particles is preferably 0.001 to 3 μm, preferably Is 0.005 to 2 μm, and the ratio (aspect ratio) of the longest length of the leaf-like silica secondary particles (plate) to the thickness is at least 10, preferably 30 or more, more preferably 50 or more, The ratio of the minimum length of the leaf-like silica secondary particles (plate) to the thickness is scaly silica having at least 2, preferably 5 or more, more preferably 10 or more. The secondary particles exist independently of each other without fusing.
[0020]
When the thickness of the leaf-like silica secondary particles is so thin as less than 0.001 μm, the mechanical strength of the particles becomes insufficient, which is not preferable. On the other hand, when the thickness is larger than 3 μm, when blended in a cosmetic, whitening or the like occurs, resulting in an unnatural finish. When the ratio of the longest length to the thickness is smaller than 10, and when the ratio of the minimum length is smaller than 2, it is not preferable because the film forming property is deteriorated. Each upper limit is not particularly specified, but the former is practically 300 or less, preferably 200 or less, and the latter is practically 150 or less, preferably 100 or less.
[0021]
As described above, the thickness and length of the leaf-like silica secondary particles referred to in the present invention mean the average value of the secondary particles unless otherwise specified.
[0022]
In the present invention, the leaf shape is sufficient if the particles have a substantially thin plate shape, and this may further be bent or twisted partially or entirely.
[0023]
The leaf-like silica secondary particles in the present invention have a very unique self-forming property due to their form, and can easily form a strong silica film even at room temperature. For example, the aqueous dispersion of leaf-like silica secondary particles used in the present invention is coated on a glass substrate and dried at room temperature, and is cured without using a film-forming agent or a film-forming aid. A tough coating is easily formed. This coating is very strong and does not easily peel off. As will be described later, this self-film-forming property has an important effect when blended in cosmetics.
[0024]
Incidentally, silica agglomerated particles (silica tertiary particles) themselves having gaps formed by such three-dimensionally irregularly overlapping secondary leaf-like silica particles are disclosed, for example, in JP-A No. 11-29317. However, it does not have at least self-film-forming properties, and even if it is added to cosmetics, it is the object of the present invention, film-forming properties (make-up sustainability). ) Is hardly expressed.
[0025]
Furthermore, conventionally, silica gel is well known as a filler for cosmetics, but silica gel particles that are amorphous porous particles having a spherical or irregular shape are used as a water slurry. When coated and dried on a substrate, a coating film is formed. However, this coating film is extremely fragile and similar to a coating film made of the aqueous dispersion of foliar silica secondary particles used in the present invention. It is a simple coating that collapses when touched lightly by hand. This is in marked contrast with the foliar secondary particles in the present invention.
[0026]
In addition, it is thought that this strong self-film-forming property of the foliar silica secondary particle used by this invention and the firmness of the formed film | membrane are based on the following reasons.
[0027]
That is, when the SEM photograph of the cross section of the coating film formed by applying and drying the aqueous dispersion of the leaf-like silica particles on the substrate is examined, the leaf-like silica secondary particles are basically the leaf-like silica secondary particles. It is constructed by laminating them in parallel, but more specifically, it is clearly recognized that the particle morphology has appropriate bends, is oriented in a bent state, and closely overlaps. It is done. In this way, it is considered that it is difficult to slide in the longitudinal direction (plane direction) because they bend each other and overlap in a wave shape. In addition, since a lot of minute irregularities are formed on the particle surface, they are entangled like ridges with each other, as if they show a locking action like an anchor or magic fastener (registered trademark), It seems that the film is also fixed in the cross-sectional direction (direction perpendicular to the longitudinal direction) and a strong film is formed as a whole.
[0028]
In addition, the secondary particles are formed by overlapping flaky primary particles, but these flaky primary particles are completely separated into individual flakes of this constituent unit by ordinary means. The leaf-like silica secondary particles are constituted by being strongly bonded and integrated with each other to such an extent that it is difficult to separate them. This is because the secondary particles are formed as constituent units (ie, so-called building blocks), and thus the cosmetic of the present invention containing the secondary silica particles is extremely excellent in makeup sustainability. It is done.
[0029]
(Preparation of leaf-like silica secondary particles)
The leaf-like silica secondary particles used in the present invention are known as so-called silica-X and silica-Y as substances, and, as already mentioned, the fine flake-like silica primary particles face each other. The particles are oriented in parallel and overlap each other to form a leaf shape.
[0030]
The foliar silica secondary particles are first obtained by hydrothermal treatment of activated silicic acid, silica sol, aerosil, silica hydrogel, silica gel (silica xerogel) and the like in the presence of an alkali metal. Is produced by forming three-dimensionally irregularly-laminated silica tertiary aggregate particles (tertiary particles), followed by various post-treatments such as crushing and drying. Can be prepared by a method of crushing and obtaining secondary silica particles. It is currently difficult to produce secondary particles directly without going through tertiary particles.
[0031]
Methods for producing tertiary particles aggregated by hydrothermal treatment are already known. For example, the method of Hydemann et al. (Beytr. Minaral. Petrogr., 10, 242-259 (1964)), the method of Mitsyuk. BA et al. (Geochem Int. 13, 101-111 (1976)), Kitahara et al. (Proc. Inst. Symp. Hydrotherm. React. 1 ^st (1983)) and any of the methods proposed by the present inventors in JP-A-11-29317, JP-A-2001-163613, and the like are preferably used. Hereinafter, although the method by which the present inventors will mainly produce the tertiary particles and further the post-treatment to produce the leaf-like silica secondary particles will be described, it is of course not limited thereto.
[0032]
In the present invention, the amount of the leaf-like silica secondary particles to be blended in the cosmetic can be changed depending on the type of cosmetics, the usage environment, and the like. It is 20 mass%, Preferably it is about 0.1-10 mass%.
[0033]
Moreover, it is preferable to mix | blend the form of a leaf-like silica by selecting any form of water slurry form, powder form, and organic medium slurry form according to the kind of cosmetics made into the said object. Each will be described in turn below.
[0034]
(Water-slurry foliar secondary particles)
First, preparation of water-slurry silica secondary particles in which leaf-like silica secondary particles are dispersed in water will be described. The water slurry of foliate silica is a preferred form when blended into water-based cosmetics such as O / W type sunscreen cream, as shown in the examples below.
[0035]
Hydrothermal treatment of the starting material such as silica hydrogel is performed by heating in a heating pressure vessel such as an autoclave to obtain silica tertiary aggregate particles, but single particles such as silica-X and silica-Y are used. In order to obtain the phase in a short time, the temperature range is preferably 150 to 220 ° C, more preferably 160 to 200 ° C. The required hydrothermal treatment time may vary depending on the hydrothermal treatment temperature, the presence or absence of seed crystals, etc., but is usually 3 to 50 hours, preferably about 5 to 40 hours.
[0036]
The silica tertiary aggregate particles thus obtained in the form of a water slurry are washed with water / solid / liquid using a solid / liquid separation / water washing apparatus such as a belt filter, and then repulped with water. ₂ The slurry is made into a water slurry having a concentration of 1 to 30% by mass and supplied to a wet pulverizer (crusher), for example, a wet bead mill, a wet ball mill, or a thin film swirl type high-speed mixer to pulverize the silica tertiary aggregate particles. A water slurry of leaf-like silica secondary particles can be obtained. Here, as the wet bead mill, it is particularly desirable to use medium beads such as alumina or zirconia having a diameter of 0.2 to 1.0 mm.
[0037]
The leaf-like silica secondary particles as a water slurry when blended in a cosmetic are desirably a water slurry dispersed in water at a concentration of 1 to 30% by mass, preferably 1 to 20% by mass. Even when a disinfectant described below is added, it is preferable to maintain this slurry concentration.
[0038]
In addition, as long as the self-film-forming property is not impaired, the leaf-like silica secondary particles in the present invention may be partially mixed with flaky primary particles or tertiary aggregate particles. .
[0039]
(Fungicide)
Basically, the water slurry of the leaf-like silica secondary particles in the present invention can be blended into the cosmetic as it is. However, it is preferable to add an appropriate bactericidal agent during the storage, during blending into cosmetics, and after blending, in order to prevent growth due to bacterial contamination. As a disinfectant that can be used, there is no particular limitation as long as it is a substance that has bactericidal, bacteriostatic and antibacterial effects and does not cause problems with the skin when blended into cosmetics. Any of them can be suitably used. The term “bactericidal agent” is used in a broad sense including so-called antibacterial agents.
[0040]
Examples of fungicides that can be used include benzoic acid, salicylic acid, propionic acid, dehydroacetic acid, sorbic acid, boric acid, chitosan, carboxylic acid, and other organic acids and salts thereof; methylparaben, ethylparaben, propylparaben, butylparaben, and the like. P-hydroxybenzoates; gallates such as octyl gallate and propyl gallate; and
[0041]
Quaternary cationic substances such as benzalkonium chloride, alkyltrimethylammonium chloride, alkyldiaminoethylglycine chloride, cetylpyridinium chloride, chlorhexidine chloride, alkylisoquinolium bromide, chlorhexidine gluconate; isopropylmethylphenol, orthophenylphenol Phenol compounds such as phenylphenol and cresol; lower alcohols such as phenoxyethanol, ethanol, isopropanol, 1,3 butylene glycol, 1,2 pentanediol and propylene glycol;
[0042]
Photosensitive elements 101, 201, 301, 401, etc .; naturally derived antibacterial substances such as hinokitiol, bisabolol, betaine;
[0043]
Others, parachlorometacresol, hexachlorophene, resorcin, tribromosaran, methylchloroisothiazolone, methylisothiazolone, imidazolidinium urea, trichlorocarbanilide, halocarban, thymol, thiram, triclosan, lauroylsacosine sodium, undecylenic acid mono Although ethanol amide etc. are illustrated, it is not limited to this.
[0044]
The addition amount of the bactericidal agent may vary depending on the type of the bactericidal agent, the efficacy, the type of the target cosmetic, and the like. Usually, the concentration in the leaf-like silica secondary particle water slurry is 0.01 to 30% by mass. More preferably, 0.03 to 20% by mass is used. If the addition amount is much less than the above value, the bactericidal action is insufficient, and if it is excessively larger than necessary, neither is preferred because the feeling of use of the cosmetic is impaired.
[0045]
(Powdered silica secondary particles)
The powdery silica secondary particles can be prepared by dehydrating and drying the water slurry-like silica secondary particles with a suitable drying device.
[0046]
That is, the water slurry of the leaf-like silica secondary particles to which no bactericidal agent is added is preferably sufficiently diluted to adjust the silica content concentration to 1-5% by mass, and the particles come into contact with each other at the time of drying and are aggregated and fixed. What is necessary is just to dry with the suitable dryer which does not have. Such a dryer may be a flash dryer, but most preferably a spray dryer (spray dryer), which is used to obtain a powder of secondary silica particles by spray drying. I can do it.
[0047]
(Organic medium slurry-like leaf-like silica secondary particles)
Moreover, the organic medium slurry in which the leaf-like silica secondary particles are dispersed in the organic medium is obtained as follows from the water slurry of the leaf-like silica secondary particles to which the above bactericidal agent is not added.
[0048]
That is, to the water slurry, after adding and mixing a water-soluble and / or water-insoluble organic medium and, if necessary, a surfactant, water is removed by a method such as evaporation (dehydration treatment), By transferring the silica particles into the organic medium material, the water slurry can be converted to an organic medium slurry.
[0049]
Thus, during the operation, the leaf-like silica secondary particles dispersed in water undergo phase transfer and are highly dispersed into the organic liquid substance in the same state as when present in water. A suitable method can be applied to the dehydration treatment (medium replacement) depending on the properties of the organic medium (organic solvent) to be converted, and is not limited to a specific method. For example, unit operations such as evaporation, distillation (reduced pressure), steam distillation (azeotropic), filtration concentration, centrifugal concentration, etc. can be applied, and industrial chemical equipment generally industrialized according to each unit operation is used. it can.
[0050]
In particular, when water and the organic medium form two layers, a distillation operation condenses the distilled vapor, separates the two layers, and then continues the operation of refluxing only the organic phase into the distillation apparatus. This makes it possible to completely replace the water in the system with an organic medium. It is also a preferable operation to supply a new organic medium during the distillation operation.
[0051]
When blending the organic medium slurry-like leaf-like silica secondary particles into the cosmetic, it is desirable that the slurry is dispersed in the organic medium at a concentration of 1 to 20% by mass, preferably 1 to 10% by mass.
[0052]
(Organic medium)
The organic medium for forming the organic medium slurry is liquid and can be separated from water by a separation operation such as distillation. In addition, the silica particles as a dispersoid can be stably dispersed in the organic medium slurry. For the convenience of handling the organic medium-based slurry, it has an appropriate boiling point and viscosity, and is not particularly limited as long as it does not cause a problem on the skin, etc., especially when blended in cosmetics. For example, the following can be used. That is,
[0053]
Ethanol, 1-propanol, 2-propanol (isopropyl alcohol), 1-butanol, 2-butanol, 2-methyl-2-propanol (t-butyl alcohol), 2-methyl-1-propanol (isobutyl alcohol), pentanol Monohydric alcohols such as
[0054]
Polyhydric alcohols such as ethylene glycol, diethylene glycol, propylene glycol;
[0055]
Aliphatic hydrocarbons such as pentane, n-hexane, n-heptane, octane, nonane, decane, undecane, dodecane, tridecane, tetradecane and pentadecane;
[0056]
Aromatic hydrocarbons such as benzene, toluene, ethylbenzene, styrene, α-methylstyrene, β-methylstyrene, chlorobenzene, dichlorobenzene, bromobenzene;
[0057]
Aliphatic ketones such as acetone, methyl ethyl ketone, methyl propyl ketone, methyl isopropyl ketone, methyl butyl ketone, methyl isobutyl ketone, pinacolone, diethyl ketone, butyrone, diisopropyl ketone;
[0058]
Aromatic ketones such as acetophenone, propiophenone, butyrophenone, valerophenone, benzophenone, dibenzyl ketone, 2-acetonaphthone;
[0059]
Ethyl ether, propyl ether, isopropyl ether, butyl ether, isobutyl ether, n-amyl ether, isoamyl ether, methyl propyl ether, methyl isopropyl ether, methyl butyl ether, methyl isobutyl ether, methyl n-amyl ether, methyl isoamyl ether, ethyl propyl ether Aliphatic ethers such as
[0060]
Glycol ethers such as ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether;
[0061]
Aromatic ethers such as anisole, phenetole, phenyl ether, benzyl ether;
[0062]
Methyl formate, ethyl formate, propyl formate, isobutyl formate, n-amyl formate, isoamyl formate, methyl acetate, ethyl acetate, isopropyl acetate, butyl acetate, isobutyl acetate, n-amyl acetate, isoamyl acetate, methyl propionate, ethyl propionate , Propyl propionate, isopropyl propionate, butyl propionate, isobutyl propionate, n-amyl propionate, crude amyl propionate, methyl butyrate, ethyl butyrate, propyl butyrate, isopropyl butyrate, butyl butyrate, isobutyl butyrate, n-amyl butyrate Fatty acid esters such as isoamyl butyrate, methyl valerate, ethyl valerate, methyl lactate, ethyl lactate, butyl lactate;
[0063]
Aromatic esters such as methyl benzoate, ethyl benzoate, methyl cinnamate, ethyl cinnamate, propyl cinnamate, methyl salicylate, ethyl salicylate, propyl salicylate, butyl salicylate, methyl phthalate, ethyl phthalate;
[0064]
Chlorinated hydrocarbons such as tetrachloroethane, trichlorethylene, perchloroethylene, dichloropropane, chlorobenzene;
[0065]
Fluorinated hydrocarbons such as 1,1,1,2-tetrafluoroethane (R-134a);
[0066]
Chlorine-containing fluorinated hydrocarbons such as 1,1-dichloro-2,2,2-trifluoroethane (R-123), monochlorodifluoromethane (R-22);
[0067]
So-called bipolar aprotic solvents such as dimethylformamide, dimethyl sulfoxide, hexamethylphosphoamide, γ-butyrolactone, β-propiolactone, ε-caprolactone, sulfolane and ethylenediamine are preferred.
[0068]
(Characteristics of secondary silica particles)
The characteristic physical properties of the leaf-like silica secondary particles in the present invention will be summarized just in case.
[0069]
The X-ray diffraction spectrum of silica in the silica secondary particles is 2θ corresponding to a card (hereinafter simply referred to as an ASTM card) number 16-0380 registered in the American ASTM (American Society for Testing and Materials). 2θ = 5.6 °, 25.8 ° and corresponding to silica-X and / or ASTM card number 31-1233, characterized by main peaks of = 4.9 °, 26.0 ° and 28.3 ° Silica composed of silica-Y characterized by a main peak at 28.3 °. As peaks other than the above, in the case of silica-X, ASTM card numbers 31-1234 and 37-0386, and in the case of silica-Y, peaks such as ASTM card numbers 35-63 and 25-1332 are recognized. is there.
[0070]
The above characteristics are useful for separation and identification of silica when a certain cosmetic containing silica is obtained. That is, when the silica is observed by SEM or TEM, this is a secondary silica particle having a specific particle size and aspect ratio defined in the present invention, and further, the X-ray diffraction spectrum indicates that this is the ASTM card number. It can be confirmed that it is a substance specified in the present invention.
[0071]
(Target cosmetics)
In the present invention, skin care cosmetics, makeup cosmetics, hair cosmetics, cleansing cosmetics, basic cosmetics, sunscreen / sunscreen cosmetics, eye cosmetics that are blended with the foliar silica secondary particles It can be suitably used for liner cosmetics, nail cosmetics, lip cosmetics, oral cosmetics, and bath cosmetics.
[0072]
That is, more specific cosmetics include skin lotions, emulsions, creams, gels, essences, sunscreen agents (sunscreen creams (O / W type or W / O type), etc.), sun oils and other skin care cosmetics. Oily cake foundation, emulsion foundation (O / W or W / O type), foundation such as cake foundation, white powder, makeup base, eye shadow, mascara, eyeliner, eyebrow, nail enamel, overcoat agent, lipstick, blusher Makeup cosmetics such as lipglow and pressed powder; hair creams, shampoos, rinses, conditioners, hair gels, hair stylings, hair treatments, hair liquids, hair conditioners, etc .; facial cleansing foams, shampoos, cleansings, packs Cleanliness such as peel off pack Such as cosmetics and the like, the dosage form is a liquid, emulsion, solid, paste, can be appropriately selected in the form of gel or the like.
[0073]
(Film-forming polymer substance)
In this invention, it is preferable to mix | blend the film-forming high molecular substance which has film formation ability with cosmetics with the leaf-like silica secondary particle.
[0074]
However, in the present invention, the main effect is the formation of a silica film due to the self-film forming property of the leaf-like silica secondary particles. That is, silica secondary particles are an essential blending component, and the film-forming polymer substance is positioned and blended as a component that assists the film forming action of the leaf-like silica secondary particles. Therefore, the film-forming polymer substance in the present invention can be added in a much smaller amount even when it is blended than in the case where it is conventionally used alone.
[0075]
Examples of the polymer substance having film-forming ability used in the present invention include acrylic resins, silicone resins, alkyd resins, carboxyvinyl polymers, olefin / maleic anhydride copolymers or salts thereof, epoxy resins, vinylpyrrolidone-based polymers, and Other polymers may be mentioned, for example, the following are preferred. For example,
[0076]
Acrylic resins include polyacrylic acid, polymethyl acrylate, polyethyl acrylate, polybutyl acrylate, polyacrylic amide, poly-N-isopropylacrylamide, ammonium polyacrylate, sodium polyacrylate, and crosslinked polyacrylic. Sodium acid, polymethacrylic acid, polymethyl methacrylate, polyethyl methacrylate, polybutyl methacrylate, polysodium methacrylate, acrylic acid / styrene / ammonium methacrylate copolymer, acrylic acid / styrene copolymer, acrylic acid / Methacrylic acid amide copolymer, alkyl acrylate / styrene copolymer, alkyl acrylate copolymer, ethyl acrylate / acrylic acid amide / acrylic acid copolymer, ethyl acrylate / butyl acrylate copolymer, acrylic Ethyl / ethyl methacrylate copolymer, ethyl acrylate / methyl methacrylate / acrylic acid copolymer, ethyl acrylate / methyl methacrylate copolymer, ethyl acrylate / methacrylic acid copolymer, octyl acrylate / styrene copolymer Polymer, octyl acrylate / vinyl acetate copolymer, hydroxypropyl acrylate / butylaminoethyl methacrylate / octylamide acrylate copolymer, butyl acrylate / hydroxyethyl methacrylate copolymer, butyl acrylate / hydroxymethacrylate Acid copolymer, butyl acrylate / methyl methacrylate copolymer, butyl acrylate / methacrylic acid copolymer, butyl acrylate / vinyl acetate copolymer, methyl acrylate / ethyl acrylate copolymer, methyl acrylate・ Styrene copolymer, a Methoxyethyl acrylate / hydroxyethyl acrylate / butyl acrylate copolymer, methoxyethyl acrylate / hydroxyethyl acrylate copolymer, acrylic resin alkanolamine, methacrylic acid / styrene copolymer, methacrylic acid / butyl methacrylate copolymer Polymer, methacrylic acid / methyl methacrylate copolymer, methyl methacrylate / butyl acrylate / octyl acrylate copolymer, etc .;
[0077]
Examples of the silicone resin include alkyl-modified silicone, oxazoline-modified silicone, dimethylsiloxane / methylcetyloxysiloxane copolymer, trimethylsiloxysilicic acid, highly polymerized methylpolysiloxane, and the like;
[0078]
Examples of alkyd resins include isophthalic acid alkyd resins, epoxy-modified phthalic acid alkyd resins, succinic acid alkyd resins, cyclohexane alkyd resins, cyclohexene alkyd resins, phthalic acid alkyd resins, and rosin modified maleic acid alkyd resins. ;
[0079]
Examples of carboxyvinyl polymers include carboxyvinyl polymers, alkyl-modified carboxyvinyl polymers, calcium salts or potassium salts thereof;
[0080]
Examples of the olefin / maleic anhydride copolymer or a salt thereof include ethylene / maleic anhydride copolymer, isobutylene / sodium maleic anhydride copolymer, and the like;
[0081]
Examples of the epoxy resin include bisphenol A type epoxy resin oleic acid ester, bisphenol A type epoxy resin stearic acid ester, bisphenol A type epoxy resin ricinoleic acid ester, epoxy resin beef tallow fatty acid ester, epoxy resin whale oil fatty acid ester and the like;
[0082]
Examples of the vinyl pyrrolidone polymer include polyvinyl pyrrolidone, vinyl pyrrolidone / styrene copolymer, vinyl pyrrolidone / vinyl acetate copolymer, vinyl pyrrolidone diethyl sulfate, N, N′-dimethylaminoethyl methacrylic acid copolymer;
[0083]
Other resins and polymers include polyvinyl alcohol, polyvinyl methyl ether, vinyl methyl ether / ethyl maleate copolymer, vinyl methyl ether / butyl maleate copolymer, styrene / methyl styrene / indene copolymer, and toluenesulfonamide resin. , Polyvinyl butyrate, polyvinyl chloride, polyvinyl acetate, vinyl acetate / crotonic acid copolymer, vinyl acetate / styrene copolymer, butadiene / acrylonitrile copolymer, and the like.
[0084]
These resins can be used alone or in combination of two or more.
[0085]
Among the film-forming polymers, those particularly preferably used in combination with the leaf-like silica secondary particles in the present invention include, for example, acrylic resins, alkyd resins, silicone resins such as trimethylsiloxysilicate, polyvinyl alcohol, and the like. By blending these in a much smaller range than before and using them together, a cosmetic film having higher oxygen permeability, no stickiness, and high film strength can be formed.
[0086]
The amount of these film-forming polymer substances to be added to the cosmetic does not need to be added so much, and is 0.001 to 30% by mass, particularly 0.005 to 20% by mass, from the point of use and stability. Is preferred.
[0087]
(Basic ingredients of cosmetics)
As a component used for the cosmetics in the present invention, any components generally used in cosmetics can be appropriately used according to the purpose within a range not impairing the object of the present invention.
[0088]
For example, colored pigments, bright pigments, organic powders, inorganic powders, surface-treated powders, tar dyes, oils, resins, surfactants, ultraviolet absorbers, fragrances, fragrances, antiseptics, bactericides, Basic components usually blended in cosmetics such as antioxidants, moisturizers, cosmetic ingredients, thickeners, physiologically active ingredients and solvents can be blended and used.
[0089]
Specifically, the following are exemplified.
That is, as powder, talc, kaolin, sericite, mica, silica, hydroxyapatite, boron nitride, ceramic powder, nylon powder, silicon powder, polyethylene powder, acrylic powder, microcrystalline cellulose, urethane powder, titanium oxide, Inorganic white pigments such as zinc oxide;
[0090]
Pearl pigments such as iron oxide (Bengara), iron titanate, yellow iron oxide, black iron oxide, ultramarine, bitumen, titanium oxide-coated mica, bismuth oxychloride, fish scale foil, colored titanium oxide-coated mica;
[0091]
Aluminum powder, Copper powder, Red 201, Red 202, Red 204, Red 205, Red 220, Red 226, Red 228, Red 405, Orange 203, Orange 204, Orange 205, Organic pigments such as yellow 401 and blue 404, red 3, red 104, red 106, red 227, red 230, red 401, red 505, orange 205, yellow 4, yellow 5 No., Yellow No. 202, Yellow No. 203, Green No. 3 and Blue No. 1 inorganic powder such as zirconium, barium or aluminum lake, organic powder, inorganic color pigment, metal powder pigment, organic color pigment and the surface of these powders Surface-treated powder with a surface coated with silicone, fluorine, metal soap, etc.
[0092]
As oil phase components, squalane, liquid paraffin, petrolatum, microcrystalline wax, ozokerite, ceresin, lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, isostearic acid, cetyl alcohol, stearyl alcohol, isostearyl alcohol, 2- Octyldodecanol, oleyl alcohol, isopropyl myristate, 2-octyldodecyl myristate, cetyl 2-ethylhexanoate, diisostearyl malate, glyceryl tri-2-ethylhexanoate, cetyl palmitate, isotridecyl isononanoate, isononane Isononyl acid, myristic acid-2-octyldodecyl, di-2-ethylhexanoic acid neopentyl glycol, tri-2-ethylhexanoic acid glycerol, oleic acid-2 -Octyldodecyl, isopropyl myristate, glycerol triisostearate, triglyceride fatty acid glycerol, candelilla wax, carnauba wax, jojoba oil, beeswax, lanolin, olive oil, camellia oil, macadamia nut oil, castor oil, methylpolysiloxane, methylphenyl Various hydrocarbons such as polysiloxane and decamethylcyclopentasiloxane, higher fatty acids, higher alcohols, esters of oils and fats, waxes, oils and fats, silicone oils, etc .;
[0093]
As surfactant, higher fatty acid soap, alkyl sulfate ester salt, polyoxyethylene alkyl ether sulfate, alkyl trimethyl ammonium chloride, dialkyl dimethyl ammonium chloride, alkyl dimethyl amino acetate betaine, alkylamido dimethyl amino acetate betaine, polyoxyethylene added higher grade Fatty alcohol, polyoxyethylene-added higher fatty acid, polyoxyethylene-added alkylphenol, polyoxyethylene-added sorbitan higher fatty acid ester, glycerin higher fatty acid ester, sorbitan higher fatty acid ester, sucrose higher fatty acid ester, lecithin and other anions, cations, amphoteric And nonionic surfactants.
[0094]
Further, as moisturizing agents, amino acids, NMF components, glycerin, propylene glycol, 1,3-butylene glycol, polyethylene glycol, sorbitol, PCA soda, etc .; as high molecular substances, proteins such as collagen, collagen derivatives, keratin degradation products, Chitin and its derivatives, chitosan and its derivatives, gum arabic, guar gum, locust bean gum, xanthan gum, carrageenan, pullulan, pectin, dextrin, quince, agar, hyaluronic acid, chondroitin sulfate, polyglutamate methyl, polyglutamate ethyl, sodium alginate and Potassium, acrylic resin and derivatives thereof, alkyl-modified silicone, oxazoline-modified silicone, dimethylsiloxane / methylcetyloxysiloxane copolymer, Limethylsiloxysilicic acid, highly polymerized methylpolysiloxane, cellulose derivatives, alkyd resins and derivatives thereof, carboxyvinyl polymers and derivatives or salts thereof, olefin / maleic anhydride copolymers or salts thereof, epoxy resins and derivatives thereof, vinyl Pyrrolidone and its derivatives, etc .;
[0095]
Plasticizers such as acetyltributyl citrate;
Various benzophenone derivatives such as oxybenzone, hydroxymethoxybenzophenonesulfonic acid, paraaminobenzoic acid, paradimethylaminobenzoic acid-2-ethylhexyl, paramethoxycinnamic acid-2-ethylhexyl, octyl salicylate, homomenthyl salicylate, paraaminobenzoic acid derivative, paramethoxysilicic acid UV absorbers such as cinnamate derivatives and salicylic acid derivatives;
[0096]
Antioxidants such as tocopherols, BHT, BHA, and gallic acid esters; sequestering agents such as ethylenediaminetetraacetic acid; and other components that are usually blended in cosmetics such as fragrances.
[0097]
There are no particular restrictions on the preparation of the cosmetic of the present invention, except that it contains leaf-like silica secondary particles in a form suitable for the target cosmetic (powder, water slurry, organic medium slurry). A known preparation method can be applied as appropriate.
[0098]
【Example】
Hereinafter, the present invention will be described in detail with reference to examples. However, these are merely examples, and the technical scope of the present invention is not construed as being limited thereto.
That is, the types of cosmetics to which the present invention is applied, and the constituents thereof are not limited to those described in the following examples, and the ingredients that are usually blended and used in cosmetics are: All can be contained without any limitation.
In the following examples and comparative examples, the blending amount of each component is mass% unless otherwise specified.
[0099]
[Reference Example 1] (Production of Silica Tertiary Aggregate Particles with Aggregated Foliar Silica Secondary Particles)
SiO ₂ / Na ₂ O = 3.0 (molar ratio), SiO ₂ A sodium silicate aqueous solution having a concentration of 21.0% by mass of 2000 ml / min and a sulfuric acid aqueous solution having a sulfuric acid concentration of 20.0% by mass are introduced into a container equipped with a discharge port from a separate inlet and instantaneously uniform. Mix and adjust the flow ratio of the two liquids so that the pH of the liquid discharged from the discharge port into the air is 7.5 to 8.0, and the silica sol solution that is uniformly mixed is continuously aired from the discharge port. Released inside. The discharged liquid became spherical droplets in the air and gelled in the air while drawing a parabola and staying for about 1 second. A water tank filled with water was placed at the fall point, and it was dropped here to age.
[0100]
After aging, the pH of the water tank was adjusted to 6 and further washed with water to obtain a silica hydrogel. The obtained silica hydrogel particles had a spherical particle shape and an average particle diameter of 6 mm. SiO in the silica hydrogel particles ₂ The mass ratio of water to mass was 4.55 times.
[0101]
The silica hydrogel particles were coarsely pulverized to an average particle size of 2.5 mm using a double roll crusher, hydrothermally treated, and silica tertiary aggregate particles were obtained as follows.
[0102]
The total SiO2 in the system is placed in an autoclave with a capacity of 50000 ml (electrically heated, with anchor-type stirring blades) ₂ / Na ₂ Silica hydrogel (SiO2) with a particle size of 2.5 mm so that the O molar ratio is 12.0. ₂ 18 mass%) 23.7 kg and sodium silicate aqueous solution (SiO ₂ 28.75% by mass, Na ₂ O9.3 mass%, SiO ₂ / Na ₂ 5.5 kg of O = 3.17 (molar ratio)) was added, 10.7 kg of ion exchange water was added thereto, and hydrothermal treatment was performed at 185 ° C. for 8 hours while stirring at 50 rpm. The total silica concentration in the system is SiO ₂ As 15% by mass.
[0103]
The slurry after the hydrothermal treatment was washed with filtered water using a filter cloth type vertical centrifuge (manufactured by Toko Machine Co., Ltd., TU-18 type), and the solid water content was 69.7% by mass (solid content concentration: 30.3). (Mass%) silica wet cake was obtained.
[0104]
When the form of the wet cake-like generated particles was observed with an SEM, it was observed that silica tertiary aggregate particles in which the leaf-like silica secondary particles aggregated three-dimensionally were formed. Further, when the particle diameter was measured by a laser diffraction / scattering particle size distribution measuring apparatus (LA-920 type, manufactured by Horiba, Ltd.), the average particle diameter was 7.2 μm.
[0105]
[Reference Example 2] (Production of water slurry of secondary silica particles)
To the wet cake 1000 g obtained in Reference Example 1 (solid content concentration: 30.3% by mass), 1020 g of ion-exchanged water is added, and an aqueous slurry of silica tertiary aggregate particles (solid content 15% by mass, pH 7. 2) 202 g was prepared.
[0106]
Next, this aqueous slurry was subjected to a shaft agitating speed of 3400 rpm and a flow rate of 10 L with a medium stirring bead mill (Dynomill KDL-PILOT A type (made by Shinmaru Enterprises Co., Ltd., vessel capacity 1.4 L, diameter 0.5 mm zirconia beads 70% filled)). / H was passed 3 times, and pulverized / dispersed to obtain a water slurry of secondary silica particles. The solid content concentration of the water slurry of the obtained leaf-like silica secondary particles was 15% by mass.
[0107]
Subsequently, ethanol and methyl parapene were added to the water slurry of the leaf-like silica secondary particles so as to have a concentration of 5% by mass and 0.15% by mass, respectively. As a result of measuring the particle size of the fine particles in the water slurry after adding the bactericidal agent, the average particle size was 1.55 μm. In addition, the average longest length of the plate relative to the thickness is 5.4 μm, the aspect ratio is 90, and the average minimum length of the plate is 1 while the average thickness of the leaf-like particles observed by SEM is 0.06 μm. The aspect ratio was 27 at .6 μm.
[0108]
Incidentally, about 100,000 bacteria / g of general bacteria were added to the water slurry of leaf-like silica secondary particles to which no bactericidal agent was added and the same water slurry to which the bactericidal agent was added as described above. When the number of general bacteria was measured after 2 weeks, almost the same value was obtained when no fungicide was added, whereas when the fungicide was added, the number of general bacteria was 0. / G.
[0109]
[Reference Example 3] (Production of leaf-like silica secondary particle powder)
7500 g of ion-exchanged water was added to 1000 g of wet cake obtained in Reference Example 1 (solid content concentration: 30.3% by mass), and again an aqueous slurry of silica tertiary aggregate particles (solid content of 3.7% by mass, pH 7). .2) was prepared 8500 g.
[0110]
This was supplied to a spray dryer and spray-dried under conditions of a hot air temperature of 300 ° C. to obtain 300 g of powder. The average particle diameter of the powder is 1.8 μm, the average thickness of the leaf-like particles observed by SEM is 0.07 μm, and the average longest length of the plate with respect to the thickness is 5.0 μm. The aspect ratio was 71, the average minimum length of the plate was 1.8 μm, and the aspect ratio was 30.
[0111]
[Reference Example 4] (Production of organic medium slurry of secondary silica particles)
Using methyl isobutyl ketone (hereinafter sometimes abbreviated as MIBK) as the organic medium, an organic medium slurry of secondary silica particles was produced. In other words, 161 g of MIBK was added to 25 g (solid content concentration: 15% by mass) of 25 g (solid content concentration: 15% by mass) of an aqueous slurry of leaf-like silica secondary particles after wet pulverization shown in Reference Example 2. In addition, it was mixed well by hand to prepare a mixed slurry of water and MIBK.
[0112]
Next, in order to azeotropically distill off the water in the mixed slurry, atmospheric pressure simple distillation was performed using a rotary evaporator (manufactured by Tokyo Rika Kikai Co., Ltd., N type). That is, 186 g of the mixed slurry was charged into a 500 ml eggplant flask, distilled for 30 minutes under the condition of an oil bath at 150 ° C., the vapor distilled off with an azeotropic composition was cooled and liquefied, and separated into two phases in a receiving tank. A separated liquid of (MIBK phase) and lower phase (aqueous phase) was obtained.
[0113]
In the receiving tank, the water phase is separated and settled in a small sphere in the upper phase (MIBK phase) and united with the lower phase (water phase), so that the water distilling status can be clearly confirmed. As the dehydration progresses, the number of separated globules (aqueous phase) gradually decreases, and when the dehydration approaches the end, the residue in the distillation flask gradually becomes viscous, and the amount of slurry adhering to the flask wall surface decreases. Increase. Therefore, 32 ml of MIBK was further added to complete the dehydration.
[0114]
The total amount of the distillate was 139 g, the upper phase (MIBK phase) was 120.3 g, and the lower phase (water phase) was 18.7 g. As a result of density measurement of each phase, the water in the upper phase is estimated to be 2%, the water in the lower phase (aqueous phase) is estimated to be 98.1%, and the amount of distilled water is estimated to be 21 g. Since the water content in the raw water slurry was about 21.3 g, it was judged that almost the entire amount was distilled.
[0115]
On the other hand, as a distillation residue, 47 g of a translucent white milky organic medium slurry (MIBK slurry) was obtained. When the solid content concentration of this slurry was measured with an infrared irradiation moisture meter (Kett Co., Ltd., FD-600), it was 7.9% by mass, and the moisture content was Karl Fischer moisture meter (Kyoto Electronics Co., Ltd., MK-AS model). ) And was 0.28% by mass.
[0116]
On the other hand, when the particle shape was observed by SEM, it was observed that it was a leaf-like silica secondary particle shape.
[0117]
Moreover, as a result of measuring the particle diameter of the fine particles in the organic medium slurry, the average particle diameter was 1.62 μm. The average thickness of the leaf-like particles observed by SEM is 0.065 μm, the average maximum length of the plate relative to the thickness is 5.3 μm, the aspect ratio is 85, and the average minimum length of the plate is 1.7 μm. The aspect ratio was 26. The solid content concentration of the MIBK dispersion of the obtained leaf-like silica secondary particles was 15% by mass.
[0118]
[Examples 1-4], [Comparative Examples 1-3] (O / W sunscreen cream)
When the leaf-like silica secondary particles (aqueous dispersion) produced in the reference example were added and not added, an O / W type sunscreen cream was prepared and evaluated as follows.
[0119]
(A) Prescription
The formulation shown in Table 1 (O / W type sunscreen cream formulation) was followed.
[0120]
(B) Manufacturing method
Mixing components (1) to (8) in Table 1 are uniformly heated and mixed, and then component (9) is added and dispersed uniformly.
Formulation components (10) to (17) are further added to the mixture of the formulation components (1) to (9), and after emulsification, the mixture is cooled to room temperature to obtain the desired sunscreen cream.
[0121]
(C) According to the said manufacturing method, the O / W type | mold sunscreen cream of Examples 1-4 and Comparative Examples 1-3 was prepared by the prescription shown in Table 1.
The obtained O / W type sunscreen cream was evaluated by the evaluation method shown in (d) below. The results are shown in Table 2.
[0122]
[Table 1]

[0123]
(D) Evaluation method
The evaluation method in the performance test of the obtained O / W type sunscreen cream is as follows.
[0124]
(I) Makeup lasting :
An O / W-type sunscreen cream was applied to form a coating film having a thickness of 20 μm on a glass plate, dried at room temperature for 15 minutes, allowed to stand for 10 minutes in a water stream, and then observed and evaluated according to the following criteria. .
[0125]
○: No change in state is observed.
Δ: Slightly peeled off.
X: It has peeled completely.
[0126]
(B) Elongation during application :
An O / W type sunscreen cream was used by 10 panelists, the following <5-level absolute evaluation> was performed, and the average score was further evaluated by the following <4-level evaluation>.
[0127]
<5-level absolute evaluation>
(Score)
Good: 5 points
Slightly good: 4 points,
Normal: 3 points
Slightly bad: 2 points
Bad: 1 point
[0128]
<4-level evaluation>
(Score)
◎: 4 points or more,
○: 3 points or more and less than 4 points
Δ: 2 or more and less than 3
×: Less than 2 points
[0129]
(C) Sealing feeling :
A use test was conducted by 10 panelists, and after 2 to 3 hours after application, the following <5-level absolute evaluation> was performed for each item, and the average score was further evaluated by the above-mentioned <4-level evaluation>.
[0130]
<5-level absolute evaluation>
(Score)
There is no sealing feeling, etc .: 6 points
There is no sealing feeling, etc .: 5 points,
There is usually a feeling of sealing: 3 points
There is a slight feeling of sealing: 2 points,
There is always a feeling of sealing: 1 point
[0131]
(D) Sticky :
In the same manner as in (c) above, a use test was conducted by 10 panelists and evaluated in the same manner.
[0132]
(E) Feeling :
In the same manner as in (c) above, a use test was conducted by 10 panelists and evaluated in the same manner.
[0133]
[Table 2]

[0134]
(E) Results and discussion
In general, O / W emulsions, such as O / W sunscreen creams, have the advantage of better usability than w / o types, where the outer phase is an oil phase, while the outer phase is an aqueous phase. Because of this, there is a problem with makeup sustainability due to sweat. Therefore, in order to improve makeup sustainability, usually a film-forming polymer is blended. It was not possible to add a sufficiently satisfactory amount.
[0135]
According to the present invention, even if the amount of the film-forming polymer to be added is not increased so much, the cosmetic sustainability, which is a conventional problem, is maintained while maintaining the properties of the O / W emulsion. It was confirmed that it could be improved.
[0136]
Moreover, since the leaf-like silica secondary particles in the present invention have film-forming properties themselves and the film is a film made of an inorganic substance, it differs from a conventional polymer film in that it is 2 to 2 after coating. Even after 3 hours, it has a smooth finish and does not feel sealed, sticky, or sticky.
[0137]
[Example 5] (Oil cake foundation)
An oily cake foundation was prepared and evaluated for the case where the leaf-like silica secondary particles (powder) produced in Reference Example 3 were added.
[0138]
(A) Prescription
The formulation shown in Table 3 was followed.
[0139]
(B) Manufacturing method
The compounding components (1) to (6) in Table 3 are uniformly pulverized. Next, the mixing components (7) to (15) are heated and mixed, and the components (1) to (6) are added and stirred uniformly.
After defoaming, the stirred product is poured into a tray and slowly cooled to room temperature to obtain the desired oily cake foundation.
[0140]
(C) Results and discussion
The oily cake foundation according to the present invention has a good makeup persistence, good elongation, and basically a film of secondary silica particles having a film forming ability itself. There was no oily feeling of use, and even after 2 to 3 hours had passed after application, it had a smooth finish with no sealing, stickiness, or feeling of stickiness.
[0141]
[Table 3]

[0142]
[Example 6] (O / W type emulsification foundation)
An O / W emulsified foundation was prepared and evaluated for the case where the leaf-like silica secondary particles (aqueous dispersion) produced in Reference Example 2 were added.
[0143]
(A) Prescription
The formulation shown in Table 4 was followed.
[0144]
(B) Manufacturing method
Ingredients (1) to (7) in Table 4 are heated and melted, and components (8) to (9) which are stirred and mixed are added and dispersed uniformly. To this, the heated and melted components (10) to (16) are gradually added for emulsification, and stirred and cooled to room temperature to obtain the desired O / W type emulsified foundation.
[0145]
(C) Results and discussion
The O / W type emulsified foundation according to the present invention has good makeup persistence due to the inorganic film of the secondary particles of foliar silica having a self-film forming property, despite having good elongation and O / W type. Even after 2 to 3 hours after application, it was a dry finish with no sealing, stickiness, or feeling of tension.
[0146]
[Table 4]

[0147]
[Example 7] (Eyeliner)
An eyeliner was prepared and evaluated for the case where the leaf-like silica secondary particles (aqueous dispersion) produced in Reference Example 2 were added.
[0148]
(A) Prescription
The formulation shown in Table 5 was followed.
[0149]
(B) Manufacturing method
Ingredients (1) to (8) in Table 5 are heated and melted, and components (9) to (10) mixed with stirring are added and dispersed uniformly, and then cooled to obtain the target eyeliner.
[0150]
(C) Results and discussion
The eyeliner according to the present invention maintains a strong cosmetic film against sweat, tears, etc., has a good elongation, and a film of secondary silica particles having a self-film-forming property makes the vinyl acetate resin emulsion feel tight and sticky. The feeling of squeezing was improved and the finish was smooth.
[0151]
[Table 5]

[0152]
[Example 8] (lipstick)
Lipstick was prepared for the case where the leaf-like silica secondary particles (powder) produced in Reference Example 3 were added, and evaluated as follows.
[0153]
(A) Prescription
The formulation shown in Table 6 was followed.
[0154]
(B) Manufacturing method
The blending components (1) to (11) in Table 6 are heated, melted and mixed and stirred uniformly.
After defoaming, the agitated material is poured into a mold and rapidly cooled to obtain the desired lipstick.
[0155]
(C) Results and discussion
The lipstick according to the present invention was not easily transferred to clothes, cups, etc., and did not feel sealed, sticky, or sticky, and had a smooth finish.
[0156]
[Table 6]

[0157]
[Example 9] (Solvent nail enamel)
A solvent-type nail enamel was prepared and evaluated for the case where the leaf-like silica secondary particles (MIBK dispersion) produced in Reference Example 4 were added.
[0158]
(A) Prescription
The formulation shown in Table 7 was followed.
[0159]
(B) Manufacturing method
Compounding components (1) to (11) in Table 7 are uniformly mixed, and components (12) to (17) are added and dispersed uniformly to obtain the desired solvent-type nail enamel.
[0160]
(C) Results and discussion
The solvent-type nail enamel according to the present invention was measured for pencil strength by the pencil strength measurement method of JIS 5600. As a result, it was confirmed that the durability was remarkably improved as compared with the non-formulated product of foliar silica secondary particles. Also, unlike the case where a film-forming resin was blended, there was no stringing, so the elongation was good, and the formed film was excellent in oxygen permeability, so there was no airtightness and a smooth finish.
[0161]
[Table 7]

[0162]
[Example 10] (W / O type mascara)
A W / O type mascara was prepared and evaluated for the case where the leaf-like silica secondary particles (powder) produced in Reference Example 3 were added.
[0163]
(A) Prescription
The formulation shown in Table 8 was followed.
[0164]
(B) Manufacturing method
Ingredients (1) to (2) in Table 8 are heated and melted, and components (3) to (5) which are stirred and mixed are added and dispersed uniformly. Heated and melted (6) to (8) are gradually added thereto to emulsify, and the mixture is stirred and cooled to room temperature. Further, (9) is added to make the whole uniform, and the desired W / O type mascara is obtained.
[0165]
(C) Results and discussion
The W / O type mascara according to the present invention maintains a strong decorative film against sweat, tears, etc., has a good elongation and has a self-film-forming film of secondary silica particles that are unique to the W / O emulsion type. The feeling of sealing and stickiness was improved and the finish was smooth.
[0166]
[Table 8]

[0167]
[Example 11] (Hair gel)
A hair gel was prepared and evaluated for the case where the leaf-like silica secondary particles (aqueous dispersion) produced in Reference Example 2 were added.
[0168]
(A) Prescription
The formulation shown in Table 9 was followed.
[0169]
(B) Manufacturing method
Ingredients (1) and (3) in Table 9 are dispersed in a part of (10). Moreover, component (2) and (4)-(9) are melt | dissolved in the remainder of a component (10). Both are mixed under stirring to obtain the desired hair gel.
[0170]
(C) Results and discussion
The hair gel according to the present invention maintained the hair styling due to the elongation to the hair and the film-forming effect of the film-forming foliar silica secondary particles, and reduced the stickiness peculiar to the water-soluble polymer, resulting in a smooth finish.
[0171]
[Table 9]

[0172]
[Example 12] (Lotion)
A lotion was prepared and evaluated for the case where the leaf-like silica secondary particles (aqueous dispersion) produced in Reference Example 2 were added.
[0173]
(A) Prescription
The formulation shown in Table 10 was followed.
[0174]
(B) Manufacturing method
The components (1) to (10) in Table 10 are uniformly stirred and mixed at room temperature to obtain the desired lotion.
[0175]
(C) Results and discussion
The basic effect of the skin lotion according to the present invention is the makeup sustainability due to the film-forming effect of the leaf-like silica secondary particles having film-forming properties. Furthermore, it was confirmed that by holding some moisture in the silanol groups on the surface of the leaf-like silica secondary particles, the water-retaining property was excellent and the finish was smooth.
[0176]
[Table 10]

[0177]
[Example 13] (Cream)
A cream was prepared and evaluated for the case where the leaf-like silica secondary particles (aqueous dispersion) produced in Reference Example 2 were added.
[0178]
(A) Prescription
The formulation shown in Table 11 was followed.
[0179]
(B) Manufacturing method
The compounding components (1) to (7) in Table 11 are heated and melted. Components (8) to (13) are gradually added to this to emulsify, and cooled to room temperature to obtain the desired cream.
[0180]
(C) Results and discussion
The cream according to the present invention, like the lotion described in Example 12, has a basic effect of makeup persistence due to the film-forming effect of the foliar secondary particles having film-forming properties. Thus, it was confirmed that the leaf-like silica secondary particles had a sealing effect and further retained a slight amount of water in the silanol groups on the surface of the leaf-like silica secondary particles.
[0181]
[Table 11]

[0182]
[Example 14] (Peel-off pack)
A peel-off pack was prepared and evaluated for the case where the leaf-like silica secondary particles (aqueous dispersion) produced in Reference Example 2 were added.
[0183]
(A) Prescription
The formulation shown in Table 12 was followed.
[0184]
(B) Manufacturing method
The blending components (1) to (8) in Table 12 are heated and mixed. To this, the components (9) to (10) mixed with stirring are added and dispersed uniformly. Components (11) to (13) are added to the dispersion, dissolved by heating, and then cooled to room temperature. Furthermore, component (14) is added to make the whole uniform, and the desired peel-off pack is obtained.
[0185]
(C) Results and discussion
The peel-off pack according to the present invention provides a strong film due to the film-forming effect of the film-forming leaf-like silica secondary particles, and like the lotion described in Example 12, the leaf-like silica 2 is blended into the peel-off pack. The secondary particles were provided with a sealing effect, and the surface silanol groups on the surface of the leaf-like silica secondary particles retained a slight amount of water, resulting in excellent water retention and a moist feeling of use.
[0186]
[Table 12]

[0187]
[Example 15] (Face Washing Foam)
A face-washing foam was prepared and evaluated for the case where the leaf-like silica secondary particles (powder) produced in Reference Example 3 were added.
[0188]
(A) Prescription
The formulation shown in Table 13 was followed.
[0189]
(B) Manufacturing method
The blending components (1) to (11) in Table 13 are heated and mixed to dissolve uniformly. Components (12) to (14) are added to this and cooled to room temperature. Thereafter, the container is filled into an appropriate container to obtain the desired facial cleansing foam.
[0190]
(C) Results and discussion
The facial cleansing foam according to the present invention had good foaming, and both usability and stability over time were good.
[0191]
That is, the basic effect of the facial cleansing foam according to the present invention is makeup sustainability due to the film-forming effect of the blended film-forming foliar silica secondary particles, but in the gaps between the blended silica secondary particles. Since the air was embraced and the bubbling was improved, there was little nuckle after washing, and the feeling of use was refreshing.
[0192]
In addition, Patent Document 1 describes a similar effect by blending spherical silica, but the face-washing foam of the present invention was much better in foaming feeling.
[0193]
[Table 13]

[0194]
[Example 16] (Shampoo)
A shampoo was prepared and evaluated for the case where the leaf-like silica secondary particles (powder) produced in Reference Example 3 were added.
[0195]
(A) Prescription
The formulation shown in Table 14 was followed.
[0196]
(B) Manufacturing method
The blending components (1) to (9) in Table 14 are heated and mixed to dissolve uniformly and cooled to room temperature to obtain the desired shampoo.
[0197]
(C) Results and discussion
The shampoo according to the present invention had good foaming as in the face-washing foam of Example 15, and both usability and stability over time were good.
[0198]
That is, in the same manner as the face-washing foam of Example 15, air was embraced in the gaps between the blended silica secondary particles, and the bubbling was improved.
[0199]
In addition, although the same effect by mix | blending spherical silica is described in patent document 1, the shampoo of this invention was more favorable in both foaming feeling.
[0200]
[Table 14]

[0201]
【The invention's effect】
As shown in the above examples, the cosmetics of the present invention are blended with secondary silica particles having self-film-forming properties. The feeling of use such as thickness, stickiness, and tension due to the sealing feeling is greatly improved, and according to the present invention, a cosmetic having excellent makeup sustainability and usability is provided.

Claims (6)

A cosmetic comprising blended foliar silica secondary particles, wherein the foliar silica secondary particles are selected from a wet slurry of silica tertiary aggregate particles from a wet bead mill, a wet ball mill, and a thin film swirl type high speed mixer. is supplied to the apparatus, a shall obtained the silica tertiary agglomerated particles to wet disintegration, flakes primary particles of scaly silica are oriented parallel manner between the surfaces to each other, overlapped plural a particle form of a laminated structure formed, and excellent cosmetic persistence, characterized in that by blending the foliar secondary silica particles having a self film-forming property capable of forming a strong silica coating film Cosmetics. A particle form of a laminated structure to be blended in the cosmetic, and the thickness of the foliar secondary silica particles having a self film-forming property is a 0.001～3Myuemu, also has an aspect ratio of at least 10 The cosmetic according to claim 1, which is as described above. The cosmetic according to claim 1, wherein the secondary particles of leaf-like silica having a particle form of a laminated structure blended with the cosmetic and having a self-forming property are in a powder form. Wherein a particle form of a laminated structure in cosmetics, and the foliar secondary silica particles having a self film-forming property is claim 1 which is a slurry obtained by dispersing in a concentration of 1 to 30 wt% in water Cosmetics described in 1. The particle-form of the laminated structure mix | blended with the said cosmetics, and the said leaf-like silica secondary particle which has a self-film-forming property is a slurry form disperse | distributed at the density | concentration of 1-20 mass% in the organic medium. Item 2. A cosmetic according to Item 1. One or more kinds of polymeric substances further comprising a film-forming ability, a particle form of the laminated structure, and, by blending as auxiliary components of the foliar secondary silica particles having a self film-forming property according Item 6. The cosmetic according to any one of Items 1 to 5.